KR101935795B1 - Method for Preparing Fuel Oil Blends Having Reduced Viscosity Using Cashew Nutshell Liquid - Google Patents

Abstract

In the present disclosure, disclosed is a method for producing a heavy oil blend having reduced viscosity, in which bio-heavy oil derived from cashew nut shell oil is mixed with petroleum heavy oil by using cashew nut shell oil and other constituent biomass-derived raw materials as feed raw materials.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for producing a heavy oil blend having reduced viscosity using cashew nut shell oil,

The present invention relates to an anti- occidentale L.) relates to a process for producing the oil-in-water blend having a reduced viscosity by the Shell Oil. More particularly, the present invention relates to a process for the preparation of a heavy oil blend having reduced viscosity by mixing biofuel heavy oil derived from cashew nut shell oil with petroleum heavy oil using cashew nut shell oil together with other biomass- And a method for manufacturing the same.

Concerns about global warming and climate change have been hampered by concerns about fossil fuel use, the introduction of carbon tax and the mandatory development of new and renewable energy, and the promotion of policies to expand the use of fossil fuels, As bio-fuels are emerging as a new and renewable energy source due to the recent instability of oil prices, depletion of fossil fuels, and environmental problems.

In this regard, bioenergy is attracting attention as an environmentally friendly energy demanded by modern society because of less environmental pollutants emission than fossil fuel. Bio-energy has a disadvantage that it costs about 1.5-2 times higher than the current energy used by coal and petroleum. However, considering the increase in social indirect costs due to environmental pollution and energy security, In developed countries such as the US, EU, and Japan, which are well aware of the necessity, they are actively implementing support policies to increase bio-energy supply. As a result, the spread of bioenergy around the world is being activated, and it is expected to continue to increase in the future.

In particular, in Korea, the Renewable Portfolio Standard (RPS) is being implemented since 2012, and the above system is based on the assumption that operators with generation facilities above a certain level will supply more than a certain amount of total generation capacity as renewable energy . As a result of these changes, power plants are using various energy sources to fulfill the obligatory supply of RPS, and bio-fuel oil is attracting attention. These biofuel oils are new and renewable energy, and they receive a renewable energy supply certificate according to the power generation rate in which conventional heavy oil is partially replaced with biofuel. In the transport sector, renewable fuel standards (RFS) are underway and in the heating sector, renewable heat obligation (RHO) is under consideration.

In this connection, biofuel refers to a product which is produced by mixing a mixture of vegetable oil (except edible oil) and fatty acid methyl (ethyl) ester, or both. C oil, a petroleum product, is composed of paraffin, naphthene, olefin, aromatic, etc., while biofuel is mainly composed of triglyceride, fatty acid and fatty acid methyl (ethyl) ester. The biofuel has a high oxidation resistance and a high reactivity because it contains a large amount of double bonds and oxygen as compared with the C oil, and has a high hygroscopic property by swelling the rubber material. In addition, low-temperature characteristics are not preferable depending on the fatty acid composition of the raw material of the biofuel feedstock, and unlike the conventional C fuel oil, unusual odor is caused.

The quality standards of the biofuel feedstock for power generation are as shown in Table 1 below.

The main feedstock of biofuel feedstock is usually purified and obtained through biodegradation / decolorization / deodorization as biomass-derived feedstocks (containing triglycerides and / or fatty acids, such as rapeseed oil and palm oil) And the oil obtained by acid treatment of the separated soap component after base neutralization is used.

However, biofuel feedstock is being used as an additive for conventional petroleum heavy oil or fuel oil rather than being used as an independent raw material. For example, US HECO has completed an empirical evaluation using a mixture of about 30 to 70% of palm oil, and it was evaluated that the overall environmental characteristics were improved by increasing the mixing ratio. In the case of Farsi, Has been utilized for power generation of diesel engines that have been partially modified.

In recent years, efforts have been made to utilize Cashew Nutshell Liquid (CNSL), which can be obtained at relatively low cost and in abundance in place of biomass-derived raw materials that have been studied as raw materials for biofuel feed oil Korean Patent No. 1778056, etc.).

Cashew nut shell oil is a phenol-based lipid obtained as a by-product in the process of obtaining fruit that is lost in cashew trees, and relatively large quantities are produced in Vietnam, India, Nigeria, Cote d'Ivoire and Brazil. The main components of cashew nut shell oil are anacadic acid, cardanol and carol, and the side chain has 15 carbon atoms.

Cashew nut shell oil is typically obtained by extraction, and is extracted after a pretreatment such as washing, drying, and grinding. At this time, hexane and / or methanol may be used as an extraction solvent, or supercritical carbon dioxide may be used. However, although the biofuel oil produced using the cashew nut shell oil meets most of the above-mentioned specifications, the iodine value ranges from approximately 210 to 240 g / 100 g, which is quite high. The iodine value is an index for measuring the oxidizing power of the engine of a power plant or a transportation vehicle. The higher the oxidizing power, the more the engine tends to corrode, which causes a problem in the stability of the engine in the long term.

On the other hand, petroleum heavy oil, specifically fuel oil, contains a large amount of bitumen and / or asphaltenes, and when it is transported through a pipe or the like, the energy required for transportation The amount of injection is inevitably increased, and even if the transfer is carried out, it causes clogging of the pipe. Although a method of adding a solvent to mitigate this phenomenon is known, it is difficult to select a suitable solvent because the asphaltene is composed of various kinds of polycyclic aromatic components and exhibits polarity, and even if a solvent is added, stability problems Thereby causing problems such as layer separation phenomenon.

In one embodiment of the present disclosure, there is provided a method for producing a biofuel heavy oil having improved properties from a biomass-derived feedstock based on cashew nut shell oil, and using the same to reduce the viscosity of petroleum heavy oil .

According to one embodiment of the present disclosure,

Producing biofuel heavy oil using cashew nut shell oil; And

Adding the biofuel heavy oil to petroleum heavy oil having a specific gravity of 0.9 to 1.2 in an amount of 10 to 30% by weight based on petroleum heavy oil;

A method for producing a heavy oil blend,

(ASTM D4294), a viscosity of 70 to 1300 mm2 / s (ASTM D445), a flash point of at least 30 DEG C (ASTM D445) D92), and a pour point of up to 30 DEG C (ASTM D97)

Wherein the step of preparing the biofuel feedstock comprises:

a) providing a biomass-derived feedstock in the form of a mixture comprising 60 to 85% by weight of a cashew nut shell oil and 40 to 15% by weight of said vegetable fatty acid feedstock;

b) feeding the biomass-derived feedstock into the reaction vessel and separately feeding the biomass-derived feedstock to the reaction vessel with the catalyst-containing alcohol-based reactant fed to the reactor from the chemical bath at a temperature of from 70 to 90 DEG C for from 0.8 to 2 hours Lt; / RTI > under stirring;

c) separating the reaction product obtained from the step b) into a sedimentation tank and precipitating the precipitate over at least 15 hours into a supernatant containing biofluid and an aggregate of impurities;

d) separating the lower layer liquid from the settling tank and transferring the lower layer liquid to the sludge tank, and transferring the upper layer liquid to a vacuum tank to remove water and remaining solvent in the upper layer liquid and purifying the same; And

e) recovering the supernatant purified in step d) as biofuel;

/ RTI >

Wherein the hydrogenation step comprises the step of hydrotreating the vegetable fatty acid raw material prior to step a), wherein the hydrogenation step comprises the steps of: And at least one selected from the group consisting of alumina, silica, silica-alumina, zirconia, ceria, titania and zeolite as the inorganic oxide support, and the hydrotreating step was at a reaction temperature of 150 to 350 ℃, hydrogen pressure of 5 to 180 bar and from 10 to 5000 Nm ³ / m ³ GOR,

The hydrogenated plant-derived fatty acid raw material contains at least 50 wt% of a fatty acid having 8-24 carbon atoms in the molecule and 8-24 carbon atoms having a double bond or a mixture thereof and the catalyst-containing alcohol-based reactant contains 100 wt% of the biomass- 7 to 9 parts by weight of a lower alcohol having 1 to 3 carbon atoms, 0.1 to 1 part by weight of an acid catalyst, and 0.05 to 0.5 part by weight of a flocculant,

The biofuel has up to 100 g / 100 g of iodine value, and

Wherein said heavy oil blend has a reduced viscosity of at least 15 mm < 2 > / s compared to said petroleum heavy oil.

The method of manufacturing heavy oil having a reduced viscosity according to a specific example of the present disclosure includes the steps of manufacturing biofuel heavy oil which can effectively overcome the limit of the conventional oil fat based on cashew nut shell oil, , And adding it to petroleum heavy oil provides an advantage that a heavy fuel oil blend having improved viscosity characteristics can be produced.

Therefore, wide commercialization is expected in the future.

1 is a process flow diagram schematically showing a series of processes for producing high quality biofuel using cashew nut shell oil according to one embodiment of the present invention.

The present invention can be all accomplished by the following description. The following description should be understood to describe preferred embodiments of the present invention, but the present invention is not necessarily limited thereto. It is to be understood that the accompanying drawings are included to provide a further understanding of the invention and are not to be construed as limiting the present invention. The details of the individual components may be properly understood by reference to the following detailed description of the related description.

The terms used in this specification can be defined as follows.

A "flash point" is generally a physical property that indicates how easily a substance or composition, typically a fluid, can be ignited or burned. Fuel having a relatively high flash point is less likely to be printed than a material having a relatively low flash point. Flash point is a performance index normally associated with safety in the storage and transportation of fuels, and is typically higher than that of petroleum heavy oil in the case of biomass-derived heavy fuels.

"Viscosity" is a physical characteristic that indicates the degree of stickiness of the fluid, and is an index related to the transfer of the fuel and the spray characteristics in the burner. As the carbon number of hydrocarbons increases and the saturated hydrocarbons increase, the viscosity of the biofuel is higher than that of the petroleum heavy oil because of the high double bond.

"Carbon residue" is an indicator of the proportion of coke-like carbide that occurs when the fuel is pyrolyzed, and the high boiling point component of the fuel has a tendency to produce carbides. The residual carbon content is an index for evaluating the combustibility, particularly with respect to the amount of carbon produced in the combustion chamber. Generally, the residual carbon content of biofuel heavy oil is lower than that of petroleum heavy oil.

"Ash content" means the amount of ash residue that remains when the fuel is combusted. During combustion, organic matter is oxidized and removed by carbon dioxide and water, and inorganic residue remaining after the removal constitutes a re-constituent. If the ash is high, accumulation of ash components in the boiler may cause maintenance problems and the emission of particulate matter (PM) may be increased.

"Copper strip corrosion" is a copper corrosion test, since sulfur compounds and acids (such as fatty acids) present in the acidic substance or fuel produced by oxidation of the fuel act as a factor of corrosion of the metal of the fuel system. And is used as an index indicating the degree of metal corrosion.

The "Acid number" is an index that increases as the oxide in the fuel increases. In the case of biofuels, oxidation reactions are more likely to occur than petroleum-based fuels based on paraffinic hydrocarbons because of the presence of double bonds. If the content of free fatty acid is increased by oxidation during storage, the material of the fuel supply system is corroded, and fuel quality is adversely affected, such as an increase in kinematic viscosity, thereby promoting the oxidation reaction. Especially, biofuel oil is more important to control the computer company because it uses low-grade copper and vegetable oils with high acid value as a raw material in order to secure economical efficiency.

"Iodine value" is an index indicating the degree of binding of iodine by breaking a double bond present in a fatty acid. Specifically, it is represented by the number of gods of iodine bound to a double bond in an unsaturated fatty acid absorbed in 100 g of fat. The iodine value is an index for measuring the oxidizing power of the engine. The higher the oxidizing power, the more corrosive the engine may cause the stability of the engine in the long term.

Cashew nut  Manufactured using shell oil Bio fuel oil

1 is a process flow diagram schematically showing a series of processes for producing high quality biofuel using cashew nut shell oil according to one embodiment of the present invention.

According to this specific example, first, each feedstock is transferred from a feedstock tank separately storing the cashew nut shell oil and the vegetable fatty acid feedstock to the reaction tank.

Cashew nut shell oil (CNSL) may be in the form of natural cashew nut shell oil and cannulated cashew nut shell oil, specifically natural cashew nut shell oil.

In an exemplary embodiment, the natural compound of cashew nut shell oil may be represented by the following general formulas (1) to (3).

As shown in the above general formulas 1 to 3, the main component of the cashew nut shell oil is a long chain aliphatic hydrocarbon bonded to an aromatic ring, wherein the aliphatic hydrocarbon has about 10 to 25 carbon atoms, specifically about 12 to 20 carbon atoms, To about 15 to 18 carbon atoms. In particular, it contains a large amount of a component containing two or more double bonds in the molecule.

In this regard, according to exemplary embodiments, the anacad acid in the natural cashew nut shell oil may be present in an amount of about 60 to 90 wt% (specifically about 65 to 85 wt%), about 3 to 7 wt% 6 wt.%), About 15 to 30 wt.% (Specifically about 17 to 25 wt.%) Of a chaldehyde and about 1 to 5 wt.% (Specifically about 2 to 4 wt.%) Of a balance component.

On the other hand, in the case of technical cashew nut shell oil, about 45 to 60 wt% (specifically about 48 to 55 wt%) of camanol, about 5 to 20 wt% (specifically about 8 to 15 wt%) of camol, To 35 wt% (specifically, about 25 to 30 wt%), and other balance components.

According to an exemplary embodiment, an organic solvent (e. G., Hexane and / or methanol) may be used to obtain a cashew nut shell oil. Alternatively, extraction using supercritical water may be performed.

 As an example, after the cashew nut shell is obtained, the extraction process may be performed after drying to remove the contained moisture to reduce the weight by about 5-10%. The volume ratio of the cashew nut shell to the organic solvent at the time of extraction may be in the range of, for example, 1: about 8 to 12, specifically about 1: about 9 to 11.

In some cases, a two-step extraction can be performed by combining extraction with organic solvent and extraction with supercritical water. As an example, extraction may be performed in an organic solvent in a first step, and extraction using supercritical water may be performed in a second step.

Alternatively, the plant-derived fatty acid raw material may be prepared, stored in a raw material tank, and then transferred or supplied to the reaction tank.

According to this specific example, the plant-derived fatty acid raw material may contain, for example, triglyceride and / or free fatty acid, and may contain 8 to 24 carbon atoms (specifically, 10 to 20 carbon atoms, more specifically, By weight of fatty acids or mixtures thereof, at least about 50% by weight, specifically at least about 60% by weight, more particularly at least about 80% by weight.

Examples of raw materials of animal fatty acids include fish oil, small oil, lard, sheep oil, butter, etc. Examples of the vegetable fatty acid raw materials include sunflower oil, canola oil, palm oil, corn oil, cottonseed oil, Almond oil, avocado oil, olive oil, camellia oil, rice bran oil, cottonseed oil, peanut oil, horseradish oil, rape oil, rice bran oil, flaxseed oil, sesame oil, sesame oil, Oil, soybean oil, castor oil, cocoa butter, palm kernel oil and the like, and the above-mentioned raw material components may be used singly or in combination. .

Exemplary compositions of raw vegetable fatty acid raw materials that can be mixed with cashew nut shell oil are shown in Tables 2 and 3 below.

fatty acid Soybean oil Corn oil Cottonseed oil Sunflower seed oil Peanut oil olive oil Rapeseed oil 14: 0 Myristic 0.4 &Lt; 0.1 0.4-2.0 <0.5 <0.4 0.05 &Lt; 1.0 16: 0 Palmitic 7-14 8 to 9 17 to 31 3 to 10 6.0 to 16 7.5-20 1.5 to 6.4 16: 1 Palmitoleic <0.5 <0.5 0.5 to 2.0 &Lt; 1.0 &Lt; 1.0 0.3 to 3.5 <3.0 18: 0 Stearic 1.4 to 5.5 0.5 to 4.0 1.0 to 4.0 1.0-10 1.3-6.5 0.5 to 3.5 0.5 to 3.1 18: 1 Oleic 19-30 19 to 50 13 to 44 14 to 65 35 to 72 56-83 8-45 18: 2 Linoleic 44 to 62 34 to 62 33-59 20-75 13-45 3.5-20 11-29 18: 3 Linolenic 4.0 to 11 <2.0 0.1 to 2.1 <0.7 &Lt; 1.0 <1.5 5 to 16 20: 0 Eicosanoic &Lt; 1.0 &Lt; 1.0 <0.7 <1.5 1.0 to 3.0 <3.0 20: 1 Eicosenoic &Lt; 1.0 <0.5 <0.5 <0.5 0.5 to 2.1 3-15 22: 0 Docosanoic <0.5 <0.5 &Lt; 1.0 1.0 to 5.0 <2.0 22: 1 Erucic <0.5 <0.5 <2.0 5 to 60 24: 0 Tetracosanoic <0.5 <0.5 <0.5 0.5 to 3.0 <2.0 24: 1 Tetracosenoic <0.5

fatty acid cocoa
butter palm oil Palm kernel oil Coconut oil butter pig
Oil Small oil 4: 0 Butyric 3.6 6: 0 Caproic <0.5 <1.2 2.2 8: 0 Caprylic 2.4 to 6.2 3.4 to 15 1.2 10: 0 Capric 2.6 to 7.0 3.2 to 15 2.8 12: 0 Lauric <1.2 41-55 41-56 2.8 14: 0 Myristic 0.1 0.5 to 5.9 14-20 13-23 10.1 2.0 2.5 14: 1 Myristoleic 3.0 16: 0 Palmitic 26.0 32-59 6.5-11 4.2-12 25.0 27.1 27.0 16: 1 Palmitoleic 0.3 <0.6 1.3 to 3.5 1.0 to 4.7 2.6 4.0 10.8 18: 0 Stearic 34.4 1.5 to 8.0 10-23 3.4-12 12.1 11.0 7.4 18: 1 Oleic 34.8 27-52 0.7 to 54 0.9 to 3.7 27.1 44.4 47.5 18: 2 Linoleic 3.0 5.0 to 14 2.4 11.4 1.7 18: 3 Linolenic 0.2 <1.5 2.1 1.1 20: 0 Eicosanoic 1.0 &Lt; 1.0 22: 0 Docosanoic 0.2

In this regard, the reason for using fatty acids or mixtures thereof within a certain range of carbon numbers (i.e., from 8 to 24) in the vegetable fatty acid feedstock is that the biofuel produced using the feed as a raw material with cashew nut shell oil is a heavy oil or a fuel oil equivalent (For example, a boiling range corresponding to C heavy oil in the case of biofuel heavy oil for power generation). When using an excessively low or high carbon number fatty acid or a mixture thereof, it is difficult to obtain properties required for heavy oil.

According to one embodiment, the above-mentioned requirements may be satisfied by one kind of fatty acid, and if necessary, two or more kinds of components may be combined to obtain the content of the fatty acid having a specific carbon number of 1 or less Be able to meet the requirements

When the content of the double bond in one or more kinds of fatty acids exceeds a certain level, the double bond existing in the molecule can be saturated by performing a hydrogenation reaction selectively before transferring to the reaction tank. For example, during the hydrotreating reaction, at least about 10%, specifically at least about 50%, and more particularly at least about 80% of the double bonds contained in the fatty acid may be saturated, and in particular, The bond may be substantially absent.

According to an illustrative embodiment, the selective hydrotreating reaction is carried out in the presence of a hydrogenation catalyst known in the art, specifically a metal selected from Groups 6, 8, 9, 10, 11 and 12 of the periodic table as hydrogenation metals, More specifically, at least one of Pt, Pd, Ni, Fe, Cu, Cr, V, Co, Mo and W may be used. Also, at least one or more of an inorganic oxide support, such as alumina, silica, silica-alumina, zirconia, ceria, titania, zeolite (for example, Y zeolite (specifically, SAR about 12 or more), clay, SAPO, According to an exemplary embodiment, the content of hydrogenation metal in the catalyst is, for example, about 0.3 to 5% by weight, specifically about 0.5 to 3% by weight, more specifically about The hydrogenation reaction may be carried out at a reaction temperature of about 150 to 350 ° C, more specifically about 270 to 250 ° C), a hydrogen pressure of about 5 to 180 bar (more specifically about 20 to 100 bar) and a GOR (H ₂ / feed ratio) of about 10 to 5000 Nm ³ / m ³ (more specifically about 300 to 1000 Nm ³ / m ³ ).

As described above, the reason for using the biomass-derived feedstock in the form of a mixture of the vegetable fatty acid raw material having a specific composition together with the cashew nut shell oil is to effectively overcome the physical limit of the bioheavy oil produced using the cashew nut shell oil It is because.

According to one embodiment, the biomass-derived feedstock may contain about 60 to 85 wt%, specifically about 65 to 80 wt%, more specifically about 70 to 75 wt%, of a cashew nut shell oil. In addition, the content of the vegetable fatty acid feedstock in the biomass-derived feedstock may range from about 40 to 15 wt%, specifically about 35 to 20 wt%, and more specifically about 30 to 25 wt%. In this connection, when the content of the vegetable fatty acid raw material exceeds the above-mentioned range, it is difficult to derive the merits of the use of the cashew nut shell oil as well as the purpose of this embodiment maximizing utilization of the cashew nut shell oil . On the other hand, when the content of the vegetable fatty acid raw material is less than the above range, problems such as the disadvantage of the bio-heavy oil based on the cashew nut shell oil, particularly, the excessive iodine value, cause the corrosion of the engine can not be solved.

Referring to FIG. 1, a biomass-derived feedstock in the form of a mixture is fed into a reactor and separately supplied with a catalyst-containing alcohol-based reactant reacting with the biomass-derived feedstock from the chemical bath.

In this connection, the catalyst-containing alcoholic reactant comprises 7 to 9 parts by weight of a lower alcohol having 1 to 3 carbon atoms, 0.1 to 1 part by weight of an acid catalyst, and 0.05 to 0.5 part by weight of a flocculant.

Specifically, as the lower alcohol, at least one selected from the group consisting of methanol, ethanol and propanol can be used. More specifically, methanol can be used. These lower alcohols can react with triglycerides and / or fatty acids contained in the biomass-derived feedstock to produce aliphatic alkyl esters (for example, by transesterification and / or esterification). In this regard, the lower alcohols can be used in about 7 to 9 parts by weight, specifically about 7.5 to 8.5 parts by weight, based on 100 parts by weight of the biomass-derived feedstock. When the amount of the lower alcohol is excessively large, the unreacted alcohol component may remain in the product in the future, resulting in lowering of the physical properties of the biofuel. On the other hand, when the amount of the lower alcohol is excessively small, The raw material component is excessively remained in the product, which not only lowers the yield of bio-heavy oil but may also cause property deterioration.

On the other hand, the acid catalyst may typically be a homogeneous catalyst, for example, at least one selected from sulfuric acid, sulfonic acid, phosphoric acid, hydrochloric acid, para toluenesulfonic acid, benzenesulfonic acid and the like, Can be used. In this connection, the acid catalyst promotes the reaction by inducing a nucleophilic attack by alcohol to protonate the carbonyl group. According to one embodiment, the amount of the acid catalyst used may range from about 0.1 to 1 part by weight, specifically about 0.2 to 0.5 part by weight, based on 100 parts by weight of the biomass-derived feedstock. If the amount of the acid catalyst used is outside the predetermined range, it may cause insufficient reaction (ester exchange reaction and / or esterification reaction) or cause excessive reaction to lower the yield of bio-heavy oil. .

In the illustrated embodiment, the catalyst-containing alcohol-based reactant may contain aggregates. Such flocculants are used to effectively separate impurities in reaction products between the biomass-derived feedstock and alcohol-based reactants by precipitation or settling, as described below. Illustratively, the flocculant may be at least one selected from the group consisting of iron sulfate, aluminum sulfate, iron chloride and aluminum chloride. However, the amount of the flocculant to be used may be about 0.05 to 0.5 parts by weight, specifically about 0.07 to 0.3 part by weight, more specifically about 0.09 to 0.2 part by weight, based on 100 parts by weight of the biomass-derived feedstock. If the amount is outside the above-mentioned range, it may be difficult to sufficiently separate the impurities in the subsequent precipitation or phase separation process, or excess aggregation may occur during the reaction to lower the reaction efficiency.

On the other hand, the catalyst-containing alcohol-based reactant may further include acetone selectively. The acetone is a protic solvent having an intermediate range of polarity, and thus has an alcohol having a relatively high polarity and a relatively low polarity It is possible to increase the miscibility between the raw materials and easily form a uniform system, thereby increasing the reaction efficiency. In this connection, the amount of acetone to be used is, for example, about 0.05 to 0.5 parts by weight, specifically about 0.07 to 0.3 part by weight, more specifically about 0.09 to 0.2 part by weight, based on 100 parts by weight of the biomass- . When the amount of acetone used is less than the above range, there is a limit in achieving the intended miscibility effect, while an excessive amount of acetone may have an undesirable effect on the reaction.

The biomass-derived feedstock introduced into the reaction tank and the catalyst-containing alcohol-based reactant react in the presence of an acid catalyst to produce biofuel. At this time, the reaction can be controlled at a temperature of about 70 to 90 ° C, specifically about 75 to 85 ° C, more specifically about 78 to 82 ° C. The temperature is a factor affecting the reaction, and it is advantageous to proceed the reaction within the temperature range described above in order to obtain the optimum reaction. Further, the reaction may be carried out under agitation for about 0.8 to 2 hours, specifically about 0.9 to 1.5 hours, more specifically about 1 to 1,2 hours.

After the reaction is carried out as described above, the reaction product is transferred to a settling tank, which is treated in a settling or stationary manner for a predetermined time to separate into a lower layer liquid containing an upper layer liquid containing bio-heavy oil and an aggregate of impurities. The separation time in the settling tank may be at least about 15 hours, specifically about 18 to 30 hours, more specifically about 20 to 25 hours. The principle of separation by precipitation or stagnation is as follows.

While the biofuel component is relatively hydrophobic, unreacted or by-products (e.g., monoglycerides, diglycerides, etc.) in the biomass-derived feedstock during reaction exhibit hydrophilicity. Therefore, biofuel oil is concentrated in the supernatant and unreacted or by-products are concentrated in the supernatant. In addition, the biomass-derived feedstock essentially contains an inorganic substance such as an alkali metal, a phosphorus (P) component derived from a phospholipid, and a metal component such as silicone mixed during the distribution process as an impurity. Therefore, the impurities are agglomerated by the coagulant added during the reaction in the preceding reaction tank, which is present in the lower layer liquid. Such a submerged solution will account for approximately 5 to 20 wt%, specifically about 7 to 15 wt%, more specifically about 10 to 12 wt% of the reaction product (liquid phase) present in the sedimentation tank.

In view of the above, in the illustrated embodiment, the bottom layer liquid is transferred to the sludge tank while the top layer liquid is transferred to the vacuum tank.

In the sludge tank, after collecting a predetermined amount of a lower layer liquid containing a large amount of unreacted materials and impurities, some components (for example, unreacted materials) are recovered or discarded according to a method known in the art. In this regard, a solvent extraction method can typically be used to recover unreacted materials. After extraction with a polar solvent (for example, ethyl acetate, ethanol or a mixture thereof), the solvent component is separated and removed So that the separated unreacted material can be recycled back into the storage tank of the biomass-derived feedstock.

On the other hand, the supernatant transferred from the settling tank to the vacuum tank contains a considerable amount (for example, about 0.1 to 10%, specifically about 1 to 7%) of water and / or residual organic solvent (specifically alcohol). Therefore, a vacuum is applied to the vacuum tank to separate moisture, which is a relatively hard component, from bio-oil, which is a target product. In this way, the moisture removed from the biofuel feedstock is removed through a filter to partially remove the impurities, and is transferred to and stored in a biofuel feedstock storage tank (biofuel feedstock recovery step).

An exemplary characteristic of the recovered biofuel is as follows.

- Flash point: at least about 120 캜, specifically at least about 150 캜, more specifically about 160 - 190 캜;

- a kinematic viscosity (50 캜): about 20 to 70 mm 2 / s, specifically about 30 to 60 mm 2 / s, more specifically about 35 to 50 mm 2 / s;

- residual carbon content: up to about 5 wt%, specifically up to about 4 wt%, more specifically about 1 to 3 wt%;

- total acid number (mgKOH / g): up to about 25, specifically up to about 23, more specifically about 18 to 21; And

- iodine (g / 100 g): up to about 100, specifically up to about 95, more specifically up to about 90.

In particular, it should be noted that the iodine value of biofuel oil is significantly reduced compared to the level of iodine (200 g / 100 g or more) of conventional cashew nut shell oil-based biofuel. Generally, biofuel has a high computation cost compared to petroleum heavy oil or fuel oil (for example, C oil), but it is possible to lower the computation cost to below the specification as the low cost raw material is increased by the reaction. Furthermore, the use of coagulant in the reaction process, separation by sedimentation tank, etc. can meet specifications in terms of inorganic impurity content, sulfur content, nitrogen content, etc., and the calorific value also satisfies the specifications required for conventional petroleum heavy oil to provide. This, as will be described later, contributes to the production of a heavily modified heavy oil by mixing with petroleum heavy oil.

Petroleum heavy oil

According to this embodiment, the petroleum heavy oil to which the biofuel feedstock is added may be a hydrocarbon oil obtained in the refinery process, for example, about 0.9 to 1.2, specifically about 0.95 to 1.15, It is a heavy oil fraction with a specific gravity of 1.1. In particular, the content of asphaltenes in petroleum heavy oil can range, for example, from about 5 to 20 wt%, specifically about 7 to 15 wt%, more specifically about 8 to 12 wt%.

In addition, the petroleum heavy oil has a sulfur content (ASTM D4294) of up to about 7 wt.% (Specifically about 0.2 to 5 wt.%, More specifically about 0.3 to 4.5 wt.%), About 70 to 1300 mm 2 / (ASTM D445) of at least about 80 to about 600 mm2 / s, more specifically about 150 to about 550 mm2 / s, at least about 30 DEG C (specifically about 60 to 250 DEG C, more specifically about 80 to 120 DEG C) ASTM D92) and a pour point (ASTM D97) of up to about 30 ° C (specifically about -15 to 20 ° C, more specifically about -10 to 15 ° C) However, it has a high specific gravity and viscosity, and has a tendency to cause occlusion in the process of transporting through a pipe or the like, due to its high pour point.

The nitrogen content in the petroleum heavy oil may be, for example, about 4000 ppm or less, specifically about 2000 ppm or less, and the CCR (Conradson Carbon Residue; ASTM D4530) may contain about 12 wt% or less, % &Lt; / RTI &gt;

Exemplary constructions of the above-described petroleum heavy oil are shown in Table 4 below.

Item Properties importance 1.115 Flash point (℃) 87 Viscosity (mm2 / s) 90 Sulfur content (% by weight) 1.27 Pour Point (℃) -1.7 Asphaltene content (% by weight) 9 Nitrogen content (ppm) 825 CCR (% by weight) 2.05

Manufacture of heavy oil blends

According to this specific example, a heavy oil blend is prepared by adding and mixing biofuel heavy oil produced using cashew nut shell oil to petroleum heavy oil. In this connection, the addition amount of biofuel is in the range of about 10 to 30% by weight, specifically about 15 to 25% by weight, more specifically about 17 to 22% by weight, based on petroleum heavy oil. At this time, blending can be performed using an agitator for easy mixing.

It should be noted that the heavy oil blend produced by adding the biofuel feedstock has a viscosity of at least about 15 mm2 / s, specifically about 20 mm2 / s, more specifically about 25 mm2 / s reduced compared to petroleum heavy oil. Further, even when about 5 days, specifically about 10 days, more specifically about 20 days, for example, at the room temperature is observed, the layer separation phenomenon of the heavy oil blend does not occur. In addition, it is possible to improve the inherent properties of the fuel oil by introducing the improved properties of the biofuel heavy oil according to the present embodiment into the petroleum heavy oil of low quality.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the present invention is not limited thereto.

Example 1

Natural cashew nut shell oil was extracted with hexane in a soxlet apparatus, and its major components and contents are shown in Table 5 below.

compound Content (% by weight) Anacardian 62.9 Cardanol 6.99 Carol 23.98 Other balance

Separately, commercially available palm oil was prepared as the vegetable fatty acid raw material, and the types and contents of the fatty acids contained in the palm oil are shown in Table 6 below.

fatty acid content Lauric acid 0.8 Myristic acid 1.9 Palmitic acid 41.5 Palmitoleic acid 0.3 Stearic acid 6.9 Oleic acid 42.3 Linoleic acid 5.3 Linolenic acid 0.4 Eicosanoic acid 0.6

Cashew nut shell oil and palm oil were transferred to the reaction tank at a ratio of 75: 25 (by weight) from the raw material tank storing each of the cashew nut shell oil and palm oil to form a mixed biomass-derived feedstock. Separately, the catalyst-containing alcohol-based reactant stored in the chemical tank was transferred to the reaction tank. At this time, the catalyst-containing alcohol-based reactant was composed of 8.5% by weight of methanol, 0.1% by weight of acetone, 0.2% by weight of sulfuric acid as a catalyst, and 0.1% by weight of a flocculant based on the mixed biomass-derived feedstock.

Then, the mixed biomass-derived feedstock and the catalyst-containing alcohol-based reactant were reacted under stirring at 90 DEG C for 1 hour. Thereafter, the reaction product was transferred to a settling tank and precipitated or allowed to stand over 24 hours to confirm the separation of the supernatant and the supernatant. At this time, the lower layer liquid was 10% by weight of the total reaction products.

Subsequently, the supernatant of the settling tank was transferred to the vacuum tank while the submerged liquid was transferred to the sludge tank and then discarded. The water and residual organic solvent contained in the supernatant were removed from the vacuum tank, solid impurities were removed using a filter, and finally the biofluid was recovered.

Comparative Example 1

A biofuel feedstock was prepared in the same manner as in Example 1, except that the biofuel feedstock was prepared using biomass-derived feedstock using only cashew nut shell oil.

Table 7 shows physical properties of bioheavy oil produced according to Example 1 and Comparative Example 1, including heavy oil standards.

Item standard Example 1 Comparative Example 1 flash point() 70 or more 182.0 187.3 Kinematic viscosity (50, / s) 15 or more, 80 or less 35.49 31.5 Residual carbon content (% by weight) below 10 2.0 1.8 Sulfur (weight%) 0.05 or less 0.03 0.03 Ash (weight%) 0.10 or less 0.03 0.03 Copper corrosion (50, 3h) 1 or less 0.92 0.95 Pour point () 27 or less 3 5 Density (15, /) 991 or less 930.2 925.3 Moisture (% by weight) 0.30 or less 0.22 0.27 Computer (KOH / g) 25 or less 20.3 23.8 alkali
(mg / kg) Na 70 or less 32 41 Ca 30 or less 6 6 K 70 or less 27 29 Iodine (g / 100 g) 120 or less 86.3 218.0 Nitrogen (% by weight) 0.3 or less 0.07 0.12 Vanadium (mg / kg) Less than 50 0.1 0.3 Total calorific value (kcal / kg) More than 9,000 39490 37588 Water and sediment (vol%) 0.5 or less 0.1 0.24 Silicon + aluminum + iron (mg / kg) 200 or less 52.4 69.3 Phosphorus (mg / kg) Below 100 15.0 25.3

According to the above table, the biofuel oil according to Comparative Example 1 satisfied most of the heavy oil specifications, but significantly exceeded the iodine standard. This is presumably because the aliphatic hydrocarbon connected to the phenolic compound, which is the main component contained in the cashew nut shell oil, contains a large number of double bonds. On the other hand, in the case of Example 1, it can be confirmed that all heavy oil standards are satisfied, and it is noteworthy that iodine value is remarkably lower than that of bio-heavy oil produced from cashew nut shell oil alone.

Example 2 and Comparative Example 2

In this example, sunflower seed oil having a relatively high double bond content in the molecule was used as the vegetable fatty acid used together with cashew nut shell oil. The content of linoleic acid (containing two double bonds) in sunflower seed oil was about 71%. Therefore, considering the results of Example 1 and Comparative Example 1, it was expected that even when used with cashew nut shell oil, high iodine value would be exhibited.

In view of the above points, in this example, bio-heavy oil was prepared in the same manner as in Example 1, except that the vegetable fatty acid raw material was separately subjected to hydrogenation treatment and then combined with cashew nut shell oil. At this time, prehydrogenation of sunflower seed oil was performed using NiMo / ZrO ₂ catalyst. The hydrogenation reaction was carried out under the reaction conditions of 200 ° C., hydrogen pressure of 20 bar, space velocity (WHSV) of 0.5 hr ^-1 and GOR of 1000 Nm ³ / m ³ to selectively remove the double bonds. The double bond contained in the oil was substantially absent.

As a result of analyzing the physical properties of the produced biomass, the iodine value of bio-heavy oil (Example 2) in case of hydrolyzing sunflower seed oil was 77.2 g / 100 g, while the bio-heavy oil (Comparative Example 2) Of iodine was 230.2 g / 100 g.

Considering the above results, it has been confirmed that a raw material which contains a large number of double bonds and is not suitable as a raw material of the vegetable fatty acid to be combined with cashew nut shell oil can also be effectively applied by hydroentanglement in advance.

Comparative Example 3

In order to confirm the effect of the addition amount of the vegetable fatty acid raw material in the biomass-derived feedstock on the properties of the biofuel, cashew nut shell oil and palm oil were transferred to the reaction tank at a ratio of 90:10 (by weight) And the resulting feedstock was formed in the same manner as in Example 1. The results are shown in Table 1. As a result of analyzing the physical properties of the produced biosynthetic stream, the iodine value was found to be 107.8 g / 100 g.

Considering the above results, when the vegetable fatty acid raw material is not mixed with the cashew nut shell oil in a predetermined amount or more, it is difficult to meet the specification of bioheavy oil due to the rise of iodine by the cashew nut shell oil, .

Example 3

100 g of petroleum oil having the properties shown in Table 4 were added and 15 g of the biofuel oil prepared according to Example 2 was added thereto while stirring at 50 DEG C (stirring rate: 100 rpm) Lt; / RTI &gt; for 1 hour to prepare a heavy oil blend.

The viscosity of the heavy oil blend prepared above was measured according to ASTM D445. As a result, the viscosity of the heavy oil blend was 62.8 mm2 / s, which was 27.2 mm2 / s lower than that of petroleum heavy oil.

Considering the above results, it can be seen that the addition of biofuel heavy oil using cashew nut shell oil improves viscosity characteristics compared with petroleum heavy oil. Further, when the heavy oil blend was visually observed at room temperature, the layer separation phenomenon did not occur even after lapse of 10 days.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the appended claims.

Claims (4)

Producing biofuel heavy oil using cashew nut shell oil; And
Adding the biofuel heavy oil to petroleum heavy oil having a specific gravity of 0.9 to 1.2 in an amount of 10 to 30% by weight based on petroleum heavy oil;
A method for producing a heavy oil blend,
(ASTM D4294), a viscosity of 70 to 1300 mm2 / s (ASTM D445), a flash point of at least 30 DEG C (ASTM D445) D92), and a pour point of up to 30 DEG C (ASTM D97)
Wherein the step of preparing the biofuel feedstock comprises:
a) providing a biomass-derived feedstock in the form of a mixture comprising 60 to 85% by weight of a cashew nut shell oil and 40 to 15% by weight of said vegetable fatty acid feedstock;
b) introducing the biomass-derived feedstock into the reaction vessel and separating the biomass-derived feedstock from the catalyst-containing alcohol-based reactant fed into the reaction tank from the chemical bath at a temperature of 70 to 90 DEG C for 0.8 to 2 hours Lt; / RTI &gt; under stirring;
c) separating the reaction product obtained from the step b) into a sedimentation tank and precipitating the precipitate over at least 15 hours into a supernatant containing biofluid and an aggregate of impurities;
d) separating the lower layer liquid from the settling tank and transferring the lower layer liquid to the sludge tank, and transferring the upper layer liquid to a vacuum tank to remove water and remaining solvent in the upper layer liquid and purifying the same; And
e) recovering the supernatant purified in step d) as biofuel;
/ RTI &gt;
Wherein the hydrogenation step comprises the step of hydrotreating the vegetable fatty acid raw material prior to step a), wherein the hydrogenation step comprises the steps of: And at least one selected from the group consisting of alumina, silica, silica-alumina, zirconia, ceria, titania and zeolite as the inorganic oxide support, and the hydrotreating step Is carried out at a reaction temperature of 150 to 350 DEG C, a hydrogen pressure of 5 to 180 bar and a GH (H ₂ / feed ratio) of 10 to 5000 Nm ³ / m ³ ,
The hydrogenated plant-derived fatty acid raw material contains at least 50 wt% of a fatty acid having 8-24 carbon atoms in the molecule and 8-24 carbon atoms having a double bond or a mixture thereof and the catalyst-containing alcohol-based reactant contains 100 wt% of the biomass- 7 to 9 parts by weight of a lower alcohol having 1 to 3 carbon atoms, 0.1 to 1 part by weight of an acid catalyst, and 0.05 to 0.5 part by weight of a flocculant,
The biofuel has up to 100 g / 100 g of iodine value, and
Wherein the heavy oil blend has a reduced viscosity of at least 15 mm &lt; 2 &gt; / s compared to the petroleum heavy oil. The method of claim 1, wherein the lower alcohol in the catalyst-containing alcohol-based reactant is at least one selected from the group consisting of methanol, ethanol, and propanol, and the acid catalyst is at least one selected from the group consisting of sulfuric acid, sulfonic acid, phosphoric acid, hydrochloric acid, para toluene sulfonic acid, Sulfonic acid, and the coagulant is at least one selected from the group consisting of iron sulfate, aluminum sulfate, iron chloride and aluminum chloride. 3. The process of claim 2 wherein the catalyst-containing alcohol-based reactant further comprises acetone,
Wherein the acetone content is in the range of 0.05 to 0.5 parts by weight based on 100 parts by weight of the biomass-derived feedstock. The method of claim 1, wherein the amount of the bottom layer formed from step c) ranges from 5 to 20% by weight of the reaction product in the settling tank.

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